Bfelamine process



April 17, 1945- A. c. WINTRINGHAM 2,373,859

MELAMINE PROCESS F11-ed April 1o, 1942 WASH WTFF /w AVM/N5 BY 24,1. f JM 'Patented Aint-1,7, v

' vMascia mouse cwinmnrnam signor to American'oyanam d Glen man, N. vJ., u-

i CompannNew: j

York, N. Y., a corporation of Maine application april 1o, 1942, serial Nm 43am 1 s claims. iwi. 26o-249.5)

This invention relates tothe manufacture of melamine by4 processes which involve the heating of cyanamide or dlcyandlamide vin a solvent comprising liquid ammonia at high'y temperatures and pressures, and more particularly to processes of this type in which thesolvent is recovered and reused. l

It is known that melamine can be obtained by heating a mixture oiy about l part of cyanamide or dicyandiamide with from l to 2 parts of liq-- uid ammonia in an autoclave, with or without the addition of a lower aliphatic alcohol orl other'` non-aqueous diluent to reduce the autoclave pres-l` sure. In the commercial operation of thisprocess it is now the practice to separate the solvent l containing the ammonia from the melamine and to pass this solvent into a stripping column wherebonate radical itself, or guanidine carbonate formed by the reaction ofammonium carbonate with the cyanamide or dicyandiamide in the autoclave,-v or to a combination of these or other factors. At any eventI found rthat the presence oi.' substantial amounts of carbon dioxide or carbonate radical in the liquid ammonia-containing solvent causes` an increase in the amount of metallic impurities in the melamineproduct and in the recirculating solvent liquor.

It is a principal object of the present invention to improve the process of melamine manufacture outlined above by obviating this source of metallic impurities.v It is a further object of in'the ammonia, or the ammonia-methanol mix- 1 ture,A can beseparated-from the wash water or other solvents thatmay be used in the process. The, recovered ammonia or yammonia-methanol mixture is then used t0 dissolve further amounts of cyanamide or dicyandiamide to prepare a newr autoclave charge.

i When a'melamine plant equipped with an autoclave composed of a high-chromium alloy steel was operated continuously for some time using the process outlined-'above with recoveryand reuse of the methanol-ammonia solvent, it lwas found that the melamine was contaminated in the autoclave by iron and other metallic impurities.

By discharging the contents of the autoclave directly into a large body of water containing an organic hydroxy compound capable offorming a complex water-soluble iron salt, as described in Patent No. 2,324,450, it was possible to retain the greater part yof the metallic impurities vin the aqueous methanol-ammonia -f solution separated from the melamine product, and during a typical weeks operation the iron content of this solution` averaged about 60 parts per million. Since extensive tests had shown that high-chromium alloy steels 'are ordinarily resistant kto attack by the reagents involved in the melamine-forming reaction, this corrosion was entirely unexpected.

After a careful investigation, I finally dscovered that the ammonia-containing solvent exhibited a tendency to pick up carbon dioxide during its reuse in the process, and that it was the carbonate radicalthat caused the corrosion resulting in an excessively high contento! iron in` the autoclave product. I have not as yet denlte- 1y determined the reason why the carbonate radical causes an increase of 'iron' in the melamine: it may be due to a corrosive action of the carthe invention to treat the ammonia-containing ysolvent; liquor after its separation from the melamine but before completion of the stripping step with va fixed in'order to remove the bonate radical therefrom.

Only a small amount of carbonate radical is present in the liquor obtained as a filtrate from theL melamine slurry formed in the autoclave, which for convenience will be referred to .hereinafter as mother liquor. Nevertheless, I found thatby adding a strong alkali such as sodium,

potassium, or calcium hydroxide to thev other liquor after its separation4 fromv the melamine butbefore the `completion -of the stripping step the content of carbonate radical could. be reduced to one-tenth of its former value, and by using a large excess of strong valkali this ligure could be reduced even further. My invention in its broader aspects, therefore, consists in the addition of a strong alkali to the mother liquor from a melamine slurry prepared by heating a charge of cyanamide or dicyandiamide in a solvent comprising liquid ammonia, followed by stripping and recovering ammoniaor a mixture of ammonia andv non-aqueous diluent substantially Y free from carbony dioxide or carbonate radical for reuse in theprocess. y 1

The invention will be illustrated in greater detail with reference to the accompanying drawing, the single ligure of which is a flow sheet :illustrating Vdiagrammatically a preferred method of recovering .a carbonate-free methanol-ammonia solution from ythe mother liquor obtained by the ltration of'a melamine slurry. In the processy outlined on this ilowsheet dicyandiamide is dissolved in a water-free mixture of methanol and ammonia from storage tank l in a mixing tank 2, and the` resulting solution is charged into an autoclave 3. In this autoclave the charge is heated at temperatures above C., and preferably above C. for several hours, the optivmum temperature range being i60-200 C. The

dicyandiamide is converted into melamine by this heat treatment, and since the melamine is not soluble in liquid ammonia or in a methanol-ammonia-mixture. it is obtained in the form of a SluIlrforder to remove small quantities of alkaline impurities of the type of guanidine, biguanide and guanylurea, the entire contents of the autoclave are discharged directly into a large volume of water in the closed quenching tank 4. A small quantity of glycerine, mannitol or other watersoluble hydroxy compound is dissolved in this water to prevent the precipitation of iron. .The ammonia and methanol from -the autoclave are of course dissolved in the water during the quenching operation, and the resulting aqueous slurry is The illter cake is washed with a quantity of cold water about equal to that used in the quenching tank 4 and the wash water is stored in a storage i tank l, from which it is introduced into the quenching tank 4 to receive the next batch of melamine from the autoclave.` The nlter cake from ammonium carbonate may be employed and the term strong alkaliis intended to define an alkali such as the oxide or hydroxide of an alkaliforming metal which is capable oi' accomplishing this result. 'I'he sodium hydroxide or other strong alkali should of course be'added in quantities `at least suillcient to combinewith all the carbonio acid radical that may be present .in the mother liquor and preferably a large `excess of strong alkali is added because of the low concentration of ammonium carbonate in. the mother liquor. Amounts on the order of 1 part by weight of NaOH for each 25-50 parts of methanol-ammonia mixture have given good results in practice.

After the strong alkali has been added the mother liquor is introduced near the center vof a stripping column 9, which is preferablyfheated by steam, in which vapors of methanol and ammonia. are separated from water containing the sodium carbonate formed in the mixing tank 8. The water and sodium carbonate are discharged to waste from the base of the' column through the outlet l while the carbonate-free ammonia and methanol' vapors ar'e y discharged througl'lV vapor line Il toa condenser I2, wherein they are condensed to a methanol-ammonia solvent liquid which is returned to the storage tankv i. By this method a `.substantially carbonate-free alcoholammonia mixture -is obtained from the liquor from the filter press Sand excessive corrosion in the autoclave 3 and' contamination of the melamine by excessive amounts of iron' are avoided. f

As a further illustration of the practical advantages obtainedby the present invention, the following -specic example is given. `A melamine plant in continuous daily production was operated on the following schedule: 150 parts by ooled to 40-70" c. and altered in s nner press 5 to separate the solvent from the melamine.-

weight of/dicyandiamide wereL dissolved in the mixing tank 2 in 270 parts of an alcohol-ammonia soution analyzing 54% ammonia and 46% methanol. 'I'his charge was then pumped into the autoclave l, which was a large autoclave composed of a chrome-iron alloy containing about 18% chromium, about 8% of nickel, about 0.2% carbon, the balance consisting substantially of iron and stabilizer for the alloy. The autoclave charge was heated at 180-200 C. for several hours at a pressure of 1600-1900 lbs./sq. in. to form a melamine slurry which was then lblown into 600 parts by weight of water containing 1 part of mannitol in the quenching tank 4 during a period of about 15 minutes. The solution in the quenchy y ing tank was agitated and cooled by recirculating through a cooler to reduce the temperature to about 40-70 C. in order to avoid excessive losses of. melaminev while retaining any unconverted dicyandiamide in solution and was then filtered in the filter press 5. The mother liquor was passed through the stripping coluinn'! and lthe alcohol and ammonia vapors were condensed in condenser I2 and returned to the storage tank I and used to dissolve more dicyandiamide to form another autoclave charge.

When the foregoing process was operated with a fresh ammonia-methanol mixture containing no carbon dioxide the amount of, iron picked up by corrosion in the autoclave was very small. However, upon continuous daily operation of the plant for a period of time without the addition of strong alkali to the mother liquor from the illter press 5 it was noted that the iron content oi' the mother liquor became progressively higher, amounting to about 62 parts per million over anaverage weeks operation. At the same time, the amount of iron in the melamine product was increased, despite the use of mannitol to hold back as much iron as possible in the quenching tank 4; during an average weeks operation without the addition of alkali to` the mother liquor the content of iron in the melamine product averaged 28 parts per million. During this period the recovered methsnol-ammonia mixture in the storage tank l was found to contain 0.043% oi' combined carbon dioxide. f

After the present invention was made, the practice was adopted of adding 5 parts by weight of sodium hydroxide for each batch of mother liquor from the quenchingtank '4 amountingto approximately 860 parts of nltered mother liquor. After the strong alkali had been added`to several successive `batches of mother liquor in this manner it 'was found that the carbonate content of thel recovered methanol-ammonia blend had-been reducedto an average of about 0.023%, and aftercontinued additions of sodium hydroxidek to successive lbatches this iigure was reduced .toas lowV as 0.0127 After the methsnol-ammonia mixture had been rendered substantially carbonate-free in this manner the average iron content of the mother liquor, over a long periodof operation, was only 27 parts per million. `At the same time the average iron content of the melamine product was reduced to 13 parts per million. 'I'he addition of a strong alkali to the mother liquor from the lter press 5 therefore resulted in a total reduction of the average iron pick up in the autoclave 3 from 90 parts per million to 40 parts per` million, with a corresponding improvement in the purity of the melamine product.

What I claim is:

1. In a melamine manufacturing process which comprises the steps of heating in an autoclave a charge consisting of a solution of a member of the group consisting of cyanamide and dicyandiamide in a liquid solvent comprising anhydrous ammonia to form melamine, separating the melamine from said solvent, and thereafter dissolving 7 further amounts of a member of the group consisting of cyanamide and dicyandiamide in said sr lvent to form another autoclave charge, the method of avoiding excessive corrosion of the autoclave d'ue to the presence of carbonate radical in said solvent which 4consists in adding to the solvent, after separating the melamine therefrom but before the new charge is formed, an alkali which combines with carbon dioxide in preference to ammonia, said alkali being added in amounts in excess of that necessary to combine with all the carbonate radical present in the solvent, and then distilling the solvent to separate it from the added alkali and the carbonate radical combined therewith. t

2. A process for the'manufacture of melamine which comprises the steps of heating a charge consisting of a solution of a member of the group consisting of cyanamide and dicyandiamide in a solvent comprising a liquid mixture of anhydrous ammonia and a non-aqueous diluent to form a melamine slurry, separating the solvent from the melamine, adding to the solvent an alkali which combines with carbon dioxide in preference to ammonia in amounts in excess of that necessary to combine with all the carbonio acid radical present, then distilling said solvent and recovering a l substantially carbonate-free mixture of anhydrous ammonia and non-aqueous diluent, and dissolving further amounts of a member of the group consisting of cyanamide and dicyandiamide consisting of cyanamide and'dicyandiamide in a f liquid mixture of anhydrous ammonia and a lower aliphatic alcohol to form a melamine slurry, discharging the slurry into water, separating the resulting aqueous solution of ammonia and alcohol from the melamine, adding an alkali which combines with carbon dioxide in preference to ammonia to the solution in amounts in excess of that necessary to combine with all the carbonio acid radical present and stripping and recovering .a substantially carbonate-free alcohol-ammonia mixture from the solution, whereby excessive l metallic impurities inthe melamine product due to the presence of the carbonate radical during the heating step are avoided.

ANDREWS C. W'INI'RINGHAM. 

